Plastic masses and process for making the same



Patented July 15, 1947 v Henry I. Gilbert, Brooklyn, N. Y.

No Drawing.

Application May 19, 194

Serial No. 487,841

14 Claims.

This invention relates to the production of plastic masses having wide utility in the arts.

Among the objects of the present invention is the production of plastic masses from relatively inexpensive materials by simple methods which plastic masses because of th'e low cost, ease of production, and properties have a wide utility in I the arts.

Other and further objects and advantages of the present invention will appear from the more detailed description set forth below, it being understood that this more detailed description is given by way of explanation and illustration only, and not; by way of limitation, since various changes therein may be made by those skilled in the art without departing from the scope and spirit of the present invention.

In accordance with the present invention, plastic masses are produced by the self-condensation of organic acid chlorides without requiring the presence or incorporation of other materials that either are polymeric or undergo polymerization in the course of the reaction.

The organic acid chlorides utilized for the purposes of this invention are most desirably the acid chlorides of the higher fatty acids such as those which are found in the natural glycerides including vegetable and animal oils and fats, as well as the acid chlorides of the acids of natural resins such as rosin specifically abietic acid, and also the acid chlorides of th acids found in waxes. The fatty acids that are utilized in accordance with this invention are desirably those having at least six carbon atoms in the molecule and more particularly the higher fatty acids such as those having at least 12 carbon atoms in the molecule. The individual acids may be used or mixtures of the acids including both mixtures of fatty acids as obtained by saponification of the natural fats and oils, or synthetic mixtures of the stated fatty acids, or mixtures of the fatty acids.

, 2 The term self-condensation refers to the fact that the condensation takes place between the mole cules of the acid chlorides whether these be mixed acid chlorides or a single acid chloride.

The condensation is desirably carried out in the presence of a solvent or vehicle-desirably one thatis inert in th'e reaction and monochlorbenzol is a desirable solvent to be employed. Other solvents that may be mentioned include nitrobenzene, carbondisulflde, brombenzene, sym-tetrachlorethane, and petroleum distillates such as ligroin and Vamolene. Diflerent solvents may exhibit different effects on the reaction or the resulting products. Thus carbon disulflde may be used where insoluble, slowly reacting materials are employed.

The materials for reaction may be mixed in any desired order and the reaction carried out at relatively low temperatures particularly inthe initial stages. The actual temperatures employed will depend on the nature of the acid chlorides being used and th type of condensation agent. In the initial stages the materials are desirably kept at a low temperature such as 5 C. and the temperature may then be raised gradually to complete the reaction. .Low initial temperatures enable better control of the reaction particularly where,

, as with resin acid chlorides, ther is intense rewith the resin acids, or mixtures of fat-acids and in the art as by treatment with phosphorus trichloride since it is the acid chlorides either alone or in admixture that are used to .produce the plastic masses.

The acid chlorides, however produced are subjected to self-condensation by the use of a condensing agent usually of the metal halide type of which aluminum chloride is the best example.

action, avoids local overheating, and generally produce more uniform products. Slow reaction tends to keep down cross-linkage and makes for more soluble products. Quick hot reactions tend to extensive cross-linkage and polymerization in more than one plane and in the direction of less soluble or insoluble products. Where less soluble products ar desired, this expedient may be used.

In cases where water is split ofl in condensation reactions, the use of higher temperatures is indicated; and also, where reacting materials are insoluble in the solvent vehicle, or where materials are utilized that do not react readily at low temperatures. So that the temperatures employed depend on the nature of the materials undergoing reaction, the catalyst employed, the nature of the solvent, and the type of product desired.

Condensation agents other than aluminum chloride can be used such as halides of iron, zinc, tin, etc. Where the action of the aluminum chloride 'is too vigorouabetter control may be obtained with one of the other condensation agents. The amount of condensing agent may have an effect on the product. Thus with small or catalytic amounts of aluminum chloride, polymerization is obtained. With molecular proportions of aluminum chloride, the tendency is toward'ketone formation initially. Ketone formation, condensation and polymerization can proceed simultaneously and in fact polymerization in some cases starts first. Other reactions also undoubtedly take place and the chemistry is involved.

While hydrochloric acid liberated during the reaction may assist the polymerization and condensation, it is desirable to remove it as rapidly as possible. Continuous stirring of the reaction mixture is, therefore utilized; and suction may also be employed thus carrying out the reaction under subatmospheri pressure.

A general method of procedure is the following. Anhydrous monochlorbenzol is placed in a reaction vessel and cooled as to 5 C. and anhydrous aluminum chloride introduced in an amount equal to about one-half of the weight based on the weight of the fatty acid chloride. The materials are mixed until thoroughly dispersed. The fatty acid chloride is then introduced slowly keeping the temperature down until all oi the acid chloride has been introduced. The temperature is then raised slowly to about 20 C. and kept at that temperature for sometime, for example, about 3 hours. The temperature is then raised to 50 C. and the reaction continued for about 3 hours longer. The reaction mixture is then drowned in a mixture of ice water and hydrochloric acid. Hydrolysis of the aluminum complex compounds is thus obtained. The monochlorbenzol is distilled off and recovered. The remaining material is heated and acidified strongly to Congo red, and thoroughly mixed as for about six hours, until all aluminum salts are dissolved. It is then filtered and the mass on the filter washed to substantial neutrality. This washed mass is then dried.

The products obtained will vary from plastic masses to hard resin-like products of very light brown to dark brown or black incolor depending on the initial materials treated and the conditions of reaction.

To illustrate the glycerides that may be used as a source of fatty acids the following may be named including such glycerides in their natural or raw, blown and heat polymerized forms: lard, tallow, neats-foot, seal, whale, menhaden. cod, cocoanut, palm kernel. peanut. olive. cotton-seed, corn, soya, palm, rape, sesame, linseed, tung. Perilla and sunflower oils and their oxidized, blown or hydrogenated, chlorinated or otherwise substituted derivatives. Among the acids that may be specifically mentioned are such acids as lauric. myristic. palmitic. stearic. oleic, erucic, behenic, linoleic, linolenic and clupanodonlc acids.

The resin acids that may be used include rosin. and other natural resins such as congo and the copals, as well as oxidized resin acids and acids from oxidized resins. The resin acid chlorides produced as herein set forth are believed to be novel products of unique utility.

The waxes include carnauba, spermaceti, beeswax, candelilla, etc.

Many industrial waste materials that contain glycerides or fatty acids or mixtures either with or without resins may be employed to be converted into acid chlorides for use in the present invention including the foots from various glyceride refining operations, tall oils containing fatty and resin acids, etc.

Thus tall oil as a waste product produced in paper making may be used, either in crude or purified form. The crude product may analyze as follows: water 2-3%, cholesterol and waxes 8%, the remainder being constituted by approx- Fish Oil Fatty Acids and Rosin Solvent {Varnolene (Petroleum thinner). Varsol ii (hydroxysolv.). Lacqder thinners (see hew Alcohol.

Acetone.

Carbon Tetrachloride. Ethylene dichloride.

Legends: s.=soluble; r. s. =readily soluble; s. s.=slightly soluble; n. s.=not soluble; v. s.=very soluble; v. s. s.=very slightly soluble; p. partially soluble.

mixture of butyl acetate, toluol, alcohol, and butyl alcohol.

While the use of fatty acid chlorides has beenspecifically emphasized, other acid chlorides may be utilized in carrying out the invention, either alone or in various admixtures, such other acid chlorides including the acid chlorides of dibasic and other polybasic aliphatic acids, both saturated and unsaturated, aromatic acids, monoand polybasic, etc. Aromatic hydrocarbons may be employed with the acid chlorides, particularly fatty acid chlorides.

Products produced in accordance with the present invention have utility in a number of ways. The products as such either by themselves or admixed with other resins and/or oils such as drying and semi-drying oils may be used in producing coatings of various types either using such materials in solution in solvents or in molten condition. They may be employed for example, for

application to concret and similar structure toand alkali resistance of products produced in accordance with the present invention make themparticularly useful for such purposes. Thus the products obtained from fish oil fatty acids andthat produced from the mixture of fish oil fatty concentrated hydrochloric acid and to hot concentrated caustic soda. Furthermore, the films produced are extremely water resistant.

This alkali resistance enables their utilization in various directions as for example, in the coating of tank cars used by caustic soda manufacturers for shipping caustic soda. The materials are resistant to hot concentrated caustic soda even of 70% solution.

While products produced in accordance with the present invention will burn, they do not burn readily unless the whole mess is made very hot and a fiame is kept in contact with it. Consequently these materials may be made relatively flame-proof by admixture with paint pigments or The lacquer thinners referred to above was a acids and rosins exhibit high resistance to hot in other related"ways and exhibit superior properties in this direction to the alkyd resins and the oils used in paints.

Materials produced in accordance with the present invention may be used for molding while heavy or thick solutions can be used for gaskets and the making of sheets.

They may be employed for backing textile materials, for compounding with other materials for flooring compositions, for waterproofing various materials, and in the production of waterproofing adhesives.

Having thus set forth my invention, I claim:

1. As a plastic mass, an inter-condensation product of mixed natural resin acid chlorides and fatty acid chlorides the acid chlorides having at least six carbon atoms in the molecule, the condensation product showing marked resistance to alkali.

2. As a plastic mass, an aluminum chloride condensation product of mixed natural resin acid chlorides with fatty acid chlorides the acid chlorides having at least six carbon atoms in the molecule.

3. A plastic mass as set forth in claim 1, in which the fatty acid chlorides are acid chlorides of the mixed acids of a natural glyceride.

4. A plastic mass as set forth in claim 2, in

which the fatty acid chlorides are acid chlorides of the mixed acids of a natural glyceride.

5. A plastic mass as set forth in claim 1, in which the resin acid chlorides are rosin acid chlorides.

6. A plastic mass as set forth in claim 2, in which the resin acid chlorides are rosin acid chlorides.

'7. A plastic mass as set forth in claim 1, including a solvent therefor.

8. A plastic mass as set forth in claim 2, in-

10. The method of making a plastic mass which consists in condensing a natural resin acid chloride with a fatty acid chloride having at least six carbon atoms in the molecule in the presence of a metal halide condensing agent and of a solvent.

11. The method of making a plastic mass which consists in condensing a natural resin acid chlowhich consists in condensing a natural resin acid 1 chloride with a fat acid chloride having at least six carbon atoms in the molecule in the presence of an aluminum chloride condensing agent and of monochlorbenzol at a temperature below C.

14. The method of making a plastic mass which consists in condensing a natural resin acid chloride with a fat acid chloride having at least six carbon atoms in the molecule in the presence of an aluminum chloride condensing agent and of monochlorbenzol at a temperature of about 5 (2., raising the temperature slowly to 20 C. for several hours, and then raising the temperature to 50 C. to complete the reaction.

HENRY I. GILBERT.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Sommer et al Mar. 21, 1939 

